JPH0575751B2

JPH0575751B2 -

Info

Publication number: JPH0575751B2
Application number: JP30640389A
Authority: JP
Inventors: Tsutayoshi Misawa; Hiroyuki Akahori; Akira Ogiso; Naoto Ito
Original assignee: Mitsui Toatsu Chemicals Inc
Current assignee: Mitsui Toatsu Chemicals Inc
Priority date: 1989-11-28
Filing date: 1989-11-28
Publication date: 1993-10-21
Also published as: JPH03167181A

Description

[Detailed description of the invention]

〔産業上の利用分野〕本発明は、色素の中間体であるアントラキノン
ジカルボン酸無水物の精製法に関する。〔従来の技術及び発明が解決しようとする課題〕１，４−ジアミノアントラキノン−２，３−ジ
カルボン酸無水物の製造方法として、１，４−ジ
アミノ−２，３−ジシアノアントラキノンを加水
分解する下式(A)の方法が“The Chemistry of
Synthetic Dyes，Volume”K.Venkataraman
著；Academic Press刊の414頁に記載されてい
る。 [Industrial Application Field] The present invention relates to a method for purifying anthraquinone dicarboxylic acid anhydride, which is an intermediate for dyes. [Prior art and problems to be solved by the invention] As a method for producing 1,4-diaminoanthraquinone-2,3-dicarboxylic acid anhydride, there is a method for producing 1,4-diaminoanthraquinone-2,3-dicyanoanthraquinone by hydrolyzing it. The method of formula (A) is “The Chemistry of
Synthetic Dyes，Volume”K.Venkataraman
Author: Academic Press, published on page 414.

【化】しかしながら、式(A)の方法には副反応として下
記式(B)の反応がおこり、[Chem] However, in the method of formula (A), the reaction of formula (B) below occurs as a side reaction,

【化】酸無水物(a)中に、イミド(b)が必ず共存するという
欠点があつた。又、酸無水物(a)、イミド(b)、いずれの化合物と
も溶媒に難溶なため、精製が出来なかつた。本発明者らは、一般式（）[C] The drawback was that the imide (b) always coexisted in the acid anhydride (a). Furthermore, both the acid anhydride (a) and the imide (b) were poorly soluble in solvents, so they could not be purified. The inventors have proposed the general formula ()

【化】（式（）中、Y¹，Y²，Y³およびY⁴は各々独
立に水素原子、アミノ基、水酸基を表わす。）で示される酸無水物を溶媒中、下記一般式（）[Chemical formula] (In formula (), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a hydrogen atom, an amino group, and a hydroxyl group.) In a solvent, an acid anhydride represented by the following general formula ()

[Means to solve the problem]

本発明者らは、一般式（） The inventors have proposed the general formula ()

【式】（式（）中、Y¹，Y²，Y³およびY⁴は各々独
立に水素原子、アミノ基、水酸基を表わす。）で示される酸無水物を溶媒中、下記一般式（）[Formula] (In formula (), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a hydrogen atom, an amino group, and a hydroxyl group.) In a solvent, an acid anhydride represented by the following general formula ()

【式】（式（）中、R¹及びR²は各々独立に炭素数
１〜10のアルキル基、アルコキシアルキル基、又
はヒドロキシアルキル基を表わす。）で示される２級アミンと反応して製造される下記
一般式（）[Formula] (In formula (), R ¹ and R ² each independently represent an alkyl group, an alkoxyalkyl group, or a hydroxyalkyl group having 1 to 10 carbon atoms.) Produced by reacting with a secondary amine represented by the following formula: The following general formula ()

〔Example〕

以下、実施例により本発明を詳しく説明する。実施例１粗１，４−ジアミノ−アントラキノン−２，３
−ジカルボン酸無水物（純度60％）200ｇ、ｎ−
ジブチルアミン125ｇをエチルセロソルブ２中、
120℃に昇温し、６時間反応した。反応後、反応
液を冷却し、濾過した後、濾液に10％塩酸水溶液
142ｇを加え、90℃に昇温し、３時間加水分解し
た後、析出した結晶を濾過し、水洗、乾燥して、
１，４−ジアミノアントラキノン−２，３−ジカ
ルボン酸無水物114ｇを得た。純度は99％であつ
た。実施例２粗１−アミノ−４−ヒドロキシアントラキノン
−２，３−ジカルボン酸無水物（純度50％）200
ｇ、ジ−（ｎ−プロピル）アミン120ｇをメチルセ
ロソルブ２中、還流下６時間反応した。反応液
を室温に冷却し、不溶物を濾別後、濾液に10％塩
酸水溶液118ｇを加え、90℃に昇温し、３時間加
水分解した後、析出した結晶を濾過、水洗、乾燥
して、１−アミノ−４−ヒドロキシアントラキノ
ン−２，３−ジカルボン酸無水物95ｇを得た。純
度は98％であつた。実施例３粗１，４−ジアミノ−５，８−ジヒドロキシア
ントラキノン−２，３−ジカルボン酸無水物（純
度50％）200ｇ、ジエタノールアミン140ｇをエチ
レングリコール２中、180℃で反応した。反応
液を室温に冷却し、不溶物を濾過した後、濾液に
10％臭化水素酸水溶液238ｇを加え、90℃に昇温
し、２時間加水分解したのち、析出した結晶を濾
過し、水洗、乾燥して１，４−ジアミノ−５，８
−ジヒドロキシアントラキノン−２，３−ジカル
ボン酸無水物95ｇを得た。純度は98％であつた。 Hereinafter, the present invention will be explained in detail with reference to Examples. Example 1 Crude 1,4-diamino-anthraquinone-2,3
-Dicarboxylic acid anhydride (purity 60%) 200g, n-
125 g of dibutylamine in ethyl cellosolve 2,
The temperature was raised to 120°C and the reaction was carried out for 6 hours. After the reaction, the reaction solution is cooled and filtered, and the filtrate is added with a 10% aqueous hydrochloric acid solution.
After adding 142 g and heating to 90°C and hydrolyzing for 3 hours, the precipitated crystals were filtered, washed with water, dried,
114 g of 1,4-diaminoanthraquinone-2,3-dicarboxylic anhydride was obtained. The purity was 99%. Example 2 Crude 1-amino-4-hydroxyanthraquinone-2,3-dicarboxylic anhydride (purity 50%) 200
120 g of di-(n-propyl)amine were reacted in methyl cellosolve 2 under reflux for 6 hours. After cooling the reaction solution to room temperature and filtering off insoluble matter, 118 g of a 10% aqueous hydrochloric acid solution was added to the filtrate, the temperature was raised to 90°C, and hydrolysis was performed for 3 hours. The precipitated crystals were filtered, washed with water, and dried. , 95 g of 1-amino-4-hydroxyanthraquinone-2,3-dicarboxylic anhydride was obtained. The purity was 98%. Example 3 200 g of crude 1,4-diamino-5,8-dihydroxyanthraquinone-2,3-dicarboxylic anhydride (purity 50%) and 140 g of diethanolamine were reacted in ethylene glycol 2 at 180°C. After cooling the reaction solution to room temperature and filtering off insoluble materials, the filtrate was
After adding 238 g of 10% hydrobromic acid aqueous solution and raising the temperature to 90°C and hydrolyzing for 2 hours, the precipitated crystals were filtered, washed with water, and dried to obtain 1,4-diamino-5,8
95 g of -dihydroxyanthraquinone-2,3-dicarboxylic anhydride was obtained. The purity was 98%.

Claims

[Claims] 1 An acid represented by the general formula () [Formula] (In the formula (), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a hydrogen atom, an amino group, or a hydroxyl group.) Anhydride in a solvent, the following general formula () [Formula] (In the formula (), R ¹ and R ² each independently represent an alkyl group, an alkoxyalkyl group, or a hydroxyalkyl group having 1 to 10 carbon atoms.) By ^reacting with ^a ^secondary amine represented by ^the ^following general formula ⁽ ⁾ , Y ⁴ and R ¹ and
R ² is the same as R ¹ and R ² in formula (). ) A method for purifying an acid anhydride represented by the formula (), characterized in that the reaction solution is filtered to remove insoluble matter, and the filtrate is hydrolyzed by adding an acid.